Materiais poliméricos (plásticos e borrachas) abrangem uma proporção continuamente crescente de resíduos urbanos e industriais descartados em aterros, seus impactos no meio ambiente são cada vez mais preocupantes. A implementação de novas tecnologias em prol da redução dos resíduos poliméricos, aceitáveis do ponto de vista ambiental e a um custo eficaz, provou ser um grande problema, face às complexidades inerentes para a reutilização dos polímeros. A radiação ionizante tem capacidade para alterar a estrutura e propriedades dos materiais poliméricos. As borrachas butílicas e halobutílicas têm sido usadas em larga escala, numa variedade de aplicações tais como partes de pneus e artefatos diversos. O principal efeito do fóton de alta energia, como raios gama nas borrachas butílicas e butílicas halogenadas é a geração de radicais livres, acompanhada por mudanças nas propriedades mecânicas. O objetivo deste trabalho é desenvolver processos de degradação controlada (desvulcanização) de borrachas butílicas e halobutílicas (cloro e bromo), de modo a caracterizar sua disponibilidade para transformação e alteração de suas propriedades. Os resultados experimentais obtidos mostraramm que as borrachas butílica e halobutílicas irradiadas a 25 kGy e posteriormente cisalhadas podem ser usadas como ponto de partida para misturas com borracha virgem. / Polymeric materials (plastics and rubbers) attain a continuous and raising proportion of urban and industrial scraps discarded in landfills; their impact on environment are more and more concerning. The implementation of new technologies in order to reduce impacts of plastic waste on the environment, at an effective cost, proved to be a great problem, due to inherent complexity for polymers re-using. Ionizing radiation is capable to modify structure and properties of polymeric material. Butyl and halobutyl rubbers have been used within a comprehensive scale, applications such as tires spare parts and diverse artifacts. The major high energy photon effect, as gamma-rays in butyl and halo butyl rubbers consists in free-radicals generation along changes in mechanical properties.This work aims to the development of controlled degradation processes (devulcanization) of butyl and halo butyl (chlorine and bromine) rubbers, in order to characterize their availability for transformation and modification of properties. Experimental results obtained showed that butyl and halobutyl rubbers,irradiated at 25 kGy and further sheared, are able to be used as an initial point for mixtures with pristine.

Synthèse de nouveaux WPU (waterborne polyurethane) cationiques à partir du caoutchouc naturel (NR), et évaluation de leurs propriétés adhésives pour des surfaces de type cuir. Ces WPU ont été obtenus par réaction du caoutchouc liquide hydroxy téléchélique (HTNR), de toluene-2,4-diisocyanate (TDI), N-methyl diethanol amine (NMDEA, en tant qu’émulsifiant) et d’éthylène glycol (EG, extenseur de chaîne). Ces structures biosourcés sont développés comme alternatives aux WPU issus des ressources fossiles à fort impact environnemental. Les effets de cinq paramètres ont été étudiés, à savoir la quantité d'émulsifiant (de 0 à 2,25 mole), celle d’éthylène glycol (de 0 à 3 moles), le Mn du HTNR (de 100 à 3000 g/mole), l'indice NCO (de 100 à 150) et le taux d’époxydation des HTNR précurseurs (de 0 à 30%). Il a été en outre démontré que la stabilité des dispersions aqueuses pour les formulations optimales dépassait les 10 mois. La géométrie des particules dispersées a été étudiée, démontrant un aspect sphérique et une taille à l'échelle nanométrique. Ainsi, plusieurs facteurs ont été étudiés pour évaluer les propriétés adhésives optimales sur bandes de cuir (Mn, pourcentage d’'époxyde). Des tests standard (Peel test et Lap Shear test) ont été utilisés et les valeurs obtenues comparées avec celles issus de formulations adhésives commerciales avec ou sans solvants. Au bilan, une formulation optimale a été déterminée (Mn = 3000 g/mole, LR epoxydation = 10%, NMDEA 5.67%wt, NCO index de 100 et 1 mole d’EG) avec cuisson préalable des systèmes à 70°C. Ce WPU a montré une force d’'adhésion supérieure à toutes les formulations commerciales testées. / Novel cationic waterborne polyurethane (cWPU) based on natural rubber (NR) have been prepared by the polymerization reaction of hydroxyl telechelic natural rubber (HTNR), toluene-2,4-diisocyanate (TDI), N-methyl diethanol amine (NMDEA, as emulsifier), and ethylene glycol (EG, chain extender). The polyol structures have been developed as alternative to produce cWPUs derived from a renewable resource. The effects of five parameters were studied – amount of NMDEA (0 – 2.25 mole), amount of EG (0 – 3 mole), molecular weight of HTNR (~1000 – 3000 g/mole), NCO index (100 – 150), and epoxide content on eHTNR soft segment (0 – 30%). The appearance of cWPU dispersion was milky-blue with long shelf life time, more than 10 months. Particle of prepared cWPU were spherical shape in the nano range size. The adhesive properties of cWPUs on the real leather surface, taking into account of the different molecular weights of HTNR and different degree of epoxide content on HTNR, were tested by lap shear test and 180 degree peel test and compared with commercial adhesives. Overall, to balance the stability and adhesive strength, the best conditions for preparing cWPU adhesive for leather application in this study was from the composition of HTNR3000 with epoxide content of 10%, NMDEA 5.67%wt, NCO index of 100 and 1 mole of EG. in condition of curing at 70 °C. In comparison to non-solvent based and solvent based commercial adhesives, the adhesive strengths of these synthesized cWPU adhesive were superior.

Materiais poliméricos (plásticos e borrachas) abrangem uma proporção continuamente crescente de resíduos urbanos e industriais descartados em aterros, seus impactos no meio ambiente são cada vez mais preocupantes. A implementação de novas tecnologias em prol da redução dos resíduos poliméricos, aceitáveis do ponto de vista ambiental e a um custo eficaz, provou ser um grande problema, face às complexidades inerentes para a reutilização dos polímeros. A radiação ionizante tem capacidade para alterar a estrutura e propriedades dos materiais poliméricos. As borrachas butílicas e halobutílicas têm sido usadas em larga escala, numa variedade de aplicações tais como partes de pneus e artefatos diversos. O principal efeito do fóton de alta energia, como raios gama nas borrachas butílicas e butílicas halogenadas é a geração de radicais livres, acompanhada por mudanças nas propriedades mecânicas. O objetivo deste trabalho é desenvolver processos de degradação controlada (desvulcanização) de borrachas butílicas e halobutílicas (cloro e bromo), de modo a caracterizar sua disponibilidade para transformação e alteração de suas propriedades. Os resultados experimentais obtidos mostraramm que as borrachas butílica e halobutílicas irradiadas a 25 kGy e posteriormente cisalhadas podem ser usadas como ponto de partida para misturas com borracha virgem. / Polymeric materials (plastics and rubbers) attain a continuous and raising proportion of urban and industrial scraps discarded in landfills; their impact on environment are more and more concerning. The implementation of new technologies in order to reduce impacts of plastic waste on the environment, at an effective cost, proved to be a great problem, due to inherent complexity for polymers re-using. Ionizing radiation is capable to modify structure and properties of polymeric material. Butyl and halobutyl rubbers have been used within a comprehensive scale, applications such as tires spare parts and diverse artifacts. The major high energy photon effect, as gamma-rays in butyl and halo butyl rubbers consists in free-radicals generation along changes in mechanical properties.This work aims to the development of controlled degradation processes (devulcanization) of butyl and halo butyl (chlorine and bromine) rubbers, in order to characterize their availability for transformation and modification of properties. Experimental results obtained showed that butyl and halobutyl rubbers,irradiated at 25 kGy and further sheared, are able to be used as an initial point for mixtures with pristine.

Made available in DSpace on 2015-04-22T22:18:28Z (GMT). No. of bitstreams: 1 Frederico Alexandre de Oliveira Lima.pdf: 1662576 bytes, checksum: 1b8d94af48801d3970da4b2e027f595c (MD5) Previous issue date: 2013-08-19 / Fundação de Amparo à Pesquisa do Estado do Amazonas / In this study, we sought to achieve, without claiming to be exhaustive, the personal experiences of workers for a segment called the Rubber Soldiers, who during the Second World War, had rallied in the wake of the agreements signed between the Brazilian Government and the U.S., aiming to increase the production of rubber, at the time the maintenance of essential military operations implemented in that context. Bring to light their perceptions and understandings about who lived and who live either on their displacements to Amazon in your life the plantation or in their urban experiences when establishing residence in Amazonian cities, associated with their struggles for recognition as subjects of a battle still unfinished. / Neste trabalho, buscou-se a alcançar, sem a pretensão de esgotar o tema, as experiências pessoais vividas por um segmento de trabalhadores chamados Soldados da Borracha, que no período da Segunda Guerra Mundial foram arregimentados no bojo dos acordos firmados entre o Governo Brasileiro e Norte- Americano, objetivando a majoração da produção de borracha, naquele momento essencial a manutenção das operações militares implementadas naquele contexto. Foi nossa intenção trazer a lume suas percepções e compreensões acerca do que viveram e do que vivem, seja nos seus deslocamentos para Amazônia, na sua vida no seringal, em suas experiências urbanas quando do estabelecimento de residência nas cidades amazônicas , seja ainda de suas lutas por reconhecimento como sujeitos de uma batalha não terminada.

Ballistic fabrics made from high performance polymeric fibers such as Kevlar®, Twaron® and Spectra® fibers and composites utilizing these fabrics are among the leading materials for modern body armor systems. Polymeric fibers used to produce ballistic fabrics often behave viscoelastically and exhibit time- and rate-dependent stress-strain relations. This necessitates the study of the constitutive behavior of composites filled by ballistic fabrics. Rheological models based on discrete rheological components (including spring and dashpot) have been widely used to study the viscoelastic behavior of polymeric fabrics. Such rheological (or viscoelasticity) models are qualitatively useful in understanding the effects of various micro-mechanisms and molecular features on the macroscopic responses of ballistic fabrics. In the present work, the constitutive behavior of Twaron CT709® fabric/natural rubber (Twaron®/NR) composite is studied using three viscoelasticity models (i.e., a four-parameter Burgers model, a three-parameter generalized Maxwell (GMn=1) model, a five-parameter generalized Maxwell (GMn=2) model) and a newly developed para-rheological model. The new model utilizes a three-parameter element to represent the Twaron® fabric and the affine network based molecular theory of rubber elasticity to account for the deformation mechanisms of the NR constituent. The uniaxial stress-strain relation of the Twaron®/NR composite at two constant strain rates is experimentally determined. The values of the parameters involved in all the models are extracted from the experimental data obtained in this study. The stress-relaxation response (under a uniaxial constant strain) and the creep deformation (under a uniaxial constant stress) of the composite are also experimentally measured. The three viscoelasticity models considered here are capable of predicting the viscoelastic constitutive behavior of the composite with different levels of accuracy. The stress-strain relation at each strain rate predicted by the newly developed para-rheological model is seen to be in good agreement with the measured stress-strain curve over the entire strain range studied. It is shown that the new model also predicts the elastic moduli and ultimate stress of the Twaron®/NR composite well. All the four models are found to predict the initial relaxation response of the composite fairly well, while the long-term stress relaxation is more accurately represented by the para-rheological model. An implicit solution provided by the para-rheological model is shown to predict the creep response of the composite more accurately than all the other models at both the primary and secondary stages. The mathematical complexity that arises from including an additional Maxwell element to the GMn=1 model to obtain the GMn=2 model with enhanced predictability is traded with the use of simple characteristic time functions in the para-rheological model. These functions are found to greatly improve the predictability of the newly developed model for the stress relaxation modulus and creep compliance. This study also explores the utility of the para-rheological model as a tool to probe the micromechanisms and molecular features that are causally related to the macroscopically observed viscoelastic behavior of the composite. The relaxation and creep trends predicted by the para-rheological model indicate that the long time viscoelastic response of the composite lies between that of a crosslinked polymer and a semi-crystalline thermoplastic.

Dans les conditions réelles d’utilisation, de multiples facteurs sont à l’origine de l’évolution des propriétés mécaniques des caoutchoucs (température, oxygène, conditions de chargement mécaniques…). Les pièces en élastomère pour l’antivibratoire automobile sont généralement massives (plusieurs millimètres d’épaisseur), le vieillissement conduit alors à des évolutions de propriétés hétérogènes. Ceci peut être induit par plusieurs mécanismes de dégradation liés, par exemple, à la présence ou non d’oxygène. Pour comprendre et identifier les mécanismes de dégradation prépondérants, une campagne de vieillissement accéléré a été menée pour une large gamme de températures représentative des conditions de service rencontrées sur véhicule (de 40°C à 120°C). De nombreux échantillons de géométries différentes (films minces, éprouvettes de caractérisation et éprouvettes de structure) ont été utilisés afin, d’une part, de faciliter l’interprétation, et d’autre part, de viser la transposition des résultats à l’échelle des pièces industrielles. L’étude présentée ici vise à identifier les mécanismes physico-chimiques et/ou évolutions microstructurales à l’origine du processus de dégradation, et de quantifier les conséquences de ceux-ci sur le comportement mécanique et les propriétés en fatigue. Ces résultats permettront de fournir les éléments nécessaires à la modélisation et la prise en compte fine des effets du vieillissement dans le processus de conception de pièces antivibratoires automobiles. / Under service conditions, many factors are responsible for the evolution of the mechanical properties of rubber parts (temperature, oxygen, mechanical loadings, etc.). Automotive anti-vibration parts using rubber-like materials are usually massive and ageing can therefore lead to heterogeneous properties. To understand the degradation process and especially the effect of oxygen, aerobic and anaerobic ageing conditions have been studied for a wide range of temperatures (from 40°C to 120°C). Numerous samples have been used with different geometries (from thin films to massive structural samples) to ease the interpretation but also to remain as close as possible from the final applications. The mechanical consequences of the ageing have been investigated for both static and fatigue properties throughout a wide experimental database (about 1000 specimens tested in fatigue, for example). The study aims at identifying the physicochemical mechanisms and/or microstructural evolution that cause the processes of degradation and to quantify the consequences on the mechanical behavior and the fatigue properties. These results will provide the necessary elements needed for the integration of thermo-oxidative effects in the fatigue design loop of automotive anti-vibration parts.

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Os estudos da epizootiologia foram realizados em Pindorama-SP e em Itiquira-MT durante dois anos. No primeiro local, constatou-se em agosto de 1998 uma epizootia de Sporothrix sp. em ninfas do percevejo. Em Itiquira, quando a infestação atingiu 56 ninfas e 18 adultos/folha, verificou-se a ocorrência natural de Sporothrix sp., reduzindo significativamente a população. Na seleção de fungos entomopatogênicos, testou-se sessenta isolados obtidos de diferentes hospedeiros e localidades sobre ninfas do 4º ínstar. Os melhores isolados foram B. bassiana (619 e 1196) com 56 e 84% de mortalidade com 3 dias após a inoculação, M. anisopliae (1144 e 1104) ambos com 90%, S. insectorum (1229) com 92% e P. fumosoroseus (1200) com 100%. Trichoderma sp., após quatro dias da inoculação causou 78% de mortalidade. Na avaliação de campo, as concentrações superiores a 10 12 e 10 13 conídios/ha foram eficientes para controle do percevejo sendo que os fungos P. fumosoroseus (1200), B. bassiana (447) e M. anisopliae (1175 e 1144) foram eficientes para controle de L. heveae. Nos estudos de toxicidade, as formulações Decis e Nuvacron foram compatíveis com B. brongniartii (619). A maioria das combinações, com exceção da formulação de Decis foi compatível com V. lecanii (972). M. anisopliae (1144) foi muito sensível para todas as formulações. Nuvacron e Stron foram compatíveis com B. bassiana (1196), P. fumosoroseus (1200) e S. insectorum (1229). Marshal foi compatível com B. bassiana (1196) e S. insectorum (1229) e Dipterex foi compatível com P. fumosoroseus (1200). Avaliou-se dois métodos de produção e dois meios de cultura para os fungos B. bassiana (1196), M. anisopliae (1189), Sporothrix insectorum (1229), Paecilomyces fumosoroseus (1200) e Verticillium lecanii (1200). Os fungos P. fumosoroseus e B. bassiana foram os que mais produziram pelo método da caixa. No método da bandeja, B. bassiana foi o fungo mais produtivo. Entre os métodos de produção testados V. lecanii produziu mais no método de bandeja e P. fumosoroseus no método da caixa. Em observações em Microscópio Eletrônico de Varredura LEO 435VP (MEV) verificou-se que em geral, todos os hifomicetos apresentaram ciclos biológicos semelhantes sobre L. heveae, tendo um período de adesão, germinação e início da penetração de 24 h, crescimento vegetativo entre 48 e 72 h, e a extrusão e conidiogênse dos patógenos em 96 h. / Studies on epizootiology were carried out in Pindorama-SP and Itiquira-MT, Brazil during two years. In Pindorama, in August 1998 an epizootic of Sporothrix sp. was observed in lacebug nymphs. In Itiquira, when the infestation reached 56 nymphs and 18 adults/leaf, a natural occurrence of Sporothrix sp. was observed, reducing significantly the pest population. Entomopathogenic fungi for use in lacebug control were selected from sixty isolates obtained from different hosts and applied to 4th instar nymphs. The best isolates were Beauveria bassiana (619 and 1196) with 56 and 84% mortality 3 days after the inoculation, Metarhizium anisopliae (1144 and 1104) both with 90%, S. insectorum (1229) with 92%, and Paecilomyces fumosoroseus (1200) with 100%. Trichoderma sp. caused 78% of mortality four days after inoculation. In field evaluations, the concentrations above 10 12 conidia/ha were efficient for control of the lacebug and the fungal isolates P. fumosoroseus (1200), B. bassiana (447) and M. anisopliae (1175 and 1144) were efficient for control of L. heveae. In the toxicity studies, the formulations Decis and Nuvacron were compatible with B. brongniartii (619). Most of the combinations, except for Decis, were compatible with Verticillium lecanii (972). M. anisopliae (1144) was very sensitive to all the formulations. Nuvacron and Stron were compatible with B. bassiana (1196), P. fumosoroseus (1200) and S. insectorum (1229). Marshal was compatible with B. bassiana (1196) and S. insectorum (1229), and Dipterex was compatible with P. fumosoroseus (1200). Two production methods and two culture media were evaluated for production of the fungi B. bassiana (1196), M. anisopliae (1189), S. insectorum (1229), P. fumosoroseus (1200) and V. lecanii (1200). The fungi P. fumosoroseus and B. bassiana were the most productive using the box method. In the tray method, B. bassiana was the most productive fungus. Between the production methods tested, V. lecanii was more productive in the tray method and P. fumosoroseus in the box method. Observations in Scanning Electronic Microscope LEO 435VP (SEM) revealed that, in general, all of the hyphomycetes had similar biological cycles on L. heveae, with adhesion, germination and beginning of the penetration within 24 h, vegetative growth between 48 and 72 h, and the extrusion and conidiogenesis of the pathogens by 96 h.

Este trabalho apresenta estudo sobre a viabilidade técnica da incorporação de borracha de pneus em ligantes asfálticos utilizados em obras de pavimentação. Trata-se de uma alternativa para solucionar um grave problema ambiental, pois no Brasil, anualmente, são descartados mais de 30 milhões de pneus, dos quais a maior parte é disposta em locais inadequados, servindo para a procriação de vetores de doenças e representando risco de contaminação do meio-ambiente. Os efeitos dos principais fatores que condicionam o comportamento do ligante asfalto-borracha (teor e granulometria da borracha, temperatura de mistura, tempo de reação) são avaliados através de ensaios tradicionais de caracterização de ligantes asfálticos e também ensaios do Método Superpave, que determinam propriedades fundamentais, diretamente relacionadas ao desempenho dos pavimentos no campo. Os resultados da análise estatística da programação fatorial de ensaios laboratoriais desenvolvida evidenciam o efeito preponderante do teor de borracha e, principalmente, que o ligante asfalto-borracha pode aumentar a resistência ao acúmulo de deformação permanente e ao aparecimento de trincas por fadiga do revestimento. / This work presents the results of a study about the technical feasibility of the use of asphalt-rubber binder by the asphalt paving industry. In Brazil, more than 30 million tires a year are disposed, mostly in inadequate sites, causing serious health and environmental problems. The effects of the main factors (rubber content, rubber particle size, temperature of mixture, reaction time) on the behavior of asphalt-rubber binders are evaluated by traditional tests and also by tests of the Superpave Method, which are based on fundamental properties, directly related to field performance. The results of the statistical analysis of the factorial design of laboratory experiments show the most significant effect of rubber content and, mainly, that asphalt-rubber binder can increase the resistance to permanent deformation and fatigue cracking.